Penicillamin-Komplexe des Nickels,Chroms und Molybdäns — Strukturelle Besonderheiten und biologische/medizinische Relevanz

Penicillamine Complexes of Nickel, Chromium, and Molybdenum — Structural Particularity and Biological/Medical Relevance The compounds Tl₂[Ni^II(H₂O)₆][Ni^II(D-pen)(L-pen)]₂[Ni^II(SCN)₂(H₂O)₄] 1 , Tl[Ni^II(D-pen)₂H] · H₂O 2 , Tl[Cr^III(D-pen)₂] 3 , and Na₂[MoO₄(pen)₂] · 3 CH₃OH · 3 H₂O 4 have been prepared by the reaction of nickel nitrate (for 1 ), nickel acetate (for 2 ), potassium chromate (for 3 ), and sodium molybdate (for 4 ) with D- and D, L-penicillamine, respectively. They were characterized by single-crystal X-ray structure analysis and other physical methods. Whereas penicillamine acts as a bidentate (N, S)-ligand in 1 and 2 , Cr^III (in 3 ), and Mo^V (in 4 ) are coordinated to the three ligand atoms N, O, and S. The presence of three different types of Ni^II-complexes a cationic, a neutral, and an anionic one in 1 is remarkable. For crystal data see Inhaltsübersicht.     

An interlaboratory capillary zone electrophoresis-UV study of various monoclonal antibodies,instruments, and ε-aminocaproic acid lots

Capillary zone electrophoresis ultraviolet (CZE-UV) has become increasingly popular for the charge heterogeneity determination of mAbs and vaccines. The ε-aminocaproic acid (eACA) CZE-UV method has been used as a rapid platform method. However, in the last years, several issues have been observed, for example, loss in electrophoretic resolution or baseline drifts. Evaluating the role of eACA on the reported issues, various laboratories were requested to provide their routinely used eACA CZE-UV methods, and background electrolyte compositions. Although every laboratory claimed to use the He et al. eACA CZE-UV method, most methods actually deviate from He's. Subsequently, a detailed interlaboratory study was designed wherein two commercially available mAbs (Waters’ Mass Check Standard mAb [pI 7] and NISTmAb [pI 9]) were provided to each laboratory, along with two detailed eACA CZE-UV protocols for a short-end, high-speed, and a long-end, high-resolution method. Ten laboratories participated each using their own instruments, and commodities, showing excellence method performance (relative standard deviations [RSDs] of percent time-corrected main peak areas from 0.2% to 1.9%, and RSDs of migration times from 0.7% to 1.8% [n = 50 per laboratory], analysis times in some cases as short as 2.5 min). This study clarified that eACA is not the main reason for the abovementioned variations.     

Binucleare Nickel(0)-Komplexe mit „Schlangenliganden”︁ vom 1-Azadientyp: Modellsysteme der oxidativen Kopplung von 1-Azadienen und 1,3-Dienen am Nickel(0)

Binuclear Nickel(0) Complexes with “Snake Ligands” of 1-Azadiene Type: Model Systems of the Oxidative Coupling of 1-Azadienes and 1.3-Dienes at Nickel(0) Synthesis, properties, and reactions of dimeric nickel(0) complexes with special 1-azadiene typ ligands (“snake ligands”) are described. The X-ray analysis of a typical compound (Bis-(bis-cinnamaldehyde-N,N'-propylendiimine)-dinickel(0)) shows that both central atoms have the coordination number 3. The four 1-azadiene groups are coordinated in a different way: unidendate coordination by N-Ni(1) bond and bidendate coordination by N-Ni(1) and olefine-Ni(2) bond. The compound is a good model system for the oxidative coupling reaction of 1-azadienes with 1.3-dienes at 2 nickel(0) centres. IR and electronic spectra show other complexes with this type of ligands to have an analogous coordination sphere.     

Some aspects of tailoring flame retardancy in HET-acid-based flame retardants

HET acid was condensed with either ethylene glycol or 1,4-butanediol to yield the respective oligoesters. These oligoesters were characterized by molecular weight, measured by vapor-pressure osmometry. The degradation mechanism of oligoesters of HET acid with either ethylene glycol or 1,4-butanediol was elucidated. The thermal properties of these polyesters were studied using differential thermal analysis and thermal volatilization analysis. The mechanism of degradation was proposed on the basis of pyrolysis–gas chromatography studies, the degradation products being subsequently identified by mass spectrometry. It turned out that in the course of decomposition, hexachlorocyclopentadiene was formed, which is believed to be the active substance for flame retardance in these systems. The aspect of tailoring flame retardancy by changing the chemical environment, i.e., by using different diols, is discussed.     

Silica nanocapsules for redox-responsive delivery

Redox-responsive silica nanocapsules with a hydrophobic liquid core were synthesized by reactive templating of miniemulsion droplets with functional alkoxysilanes. Tetrasulfide bridges were successfully introduced into the inorganic shell and were found to be accessible for chemical reactions as shown by ³¹P-NMR spectroscopy. Indeed, the tetrasulfide groups could be reduced to yield thiol groups. A subsequent increase of permeability of the silica shell was observed upon reduction of the tetrasulfide groups.     

Thermal investigation of PEG 4000 — oxazepam binary system

A thermal study using DSC and Hot Stage Microscopy (HSM) was carried out to investigate the interaction in solid state of the binary system PEG 4000 — oxazepam, and to establish their phase diagram. The eutectic composition, which melting occurs at lower temperature as compared with the pure components, has been determined. The results obtained by DSC and HSM have indicated that PEG 4000 — oxazepam mixtures displays no obvious incompatibilities, and that the system shows a typical eutectic behaviour. However because of the closeness of the melting of PEG 4000 to the eutectic temperature, it was difficult to determine precisely the eutectic composition and temperature on the basis of DSC measurements alone. The use of heats of fusion corresponding to physical mixtures allowed an estimation of the eutectic composition at 6% w/w oxazepam. Additional information of temperature (57.6C) and composition (5–10% w/w oxazepam) of the eutectic was obtained by HSM using the contact method. This low melting temperature in this range of compositions offers advantages in terms of drug stability and easy manufacture.     

One-dimensional magnetism and crystal structure ofcatena-di-bromobis(3,5-dimethylpyridine)copper(II)

Summary Crystals ofcatena-di--bromobis(3,5-dimethylpyridine)copper(II) are monoclinic, space group P2₁/a. The unit cell constants area=13.900(2),b=14.416(2),c=4.097(1) Å,=93.49(2)°, V=819.4 ų and Z=2. The structure was determined from powder data using a Guinier-Johansson focussing powder camera. The structure was solved using a simplex method for function minimization to a conventional R-value of 0.13.The structure consists of infinite linear chains parallel toc in which the copper coordination is distorted elongated octahedral. Cu-Br distances were found to be 2.449(7) and 3.286(7) Å, whereas the Cu-N bond length is 2.02(2) Å. All distances are in the range usually observed for this type of compounds.The antiferromagnetic superexchange interactions between adjacent Cu^II ions (J = –21 cm^–1) has been compared with those observed in structural similar CuBr₂L₂ compounds. The differences in observed J-values are discussed briefly, in relation to the structural variations. It appears that very small changes in structural parameters strongly affect the magnetic exchange.